Sulfonic acid surface active agent and method of preparation



Patented Apr. 10, 1951 SULFONIC ACID SURFACE ACTIVE'AGENT AND METHOD OF PREPARATION G len W. Hedrick, Glen Ellyn, 111., assignor to.

'E. F. Houghton and Company, Philadelphia, 7

Pa. a corporation of Pennsylvania No Drawing.

Th P es n inventi n re a teno e sur c active agents and more particularly, it relates to sur ac active a ent ha in ma k d et properties, as well as other desirable properties,

comprising a new type of chemical substance,

pro de s a e act e agents hav n o ta ins e t n o erties wh ch agents y ba whe e e su h opert e a sir r 16X.- a pl i oce ing t xtil fi es and fabrics, leather, paper, and other fibrous materials, in cleaning processes, such as general household cleanin mate ia ea ing i wash ne, d th lik nd i fr hina emu s y g, emul on agents are especially useful to increase the water-absorptivity of fibrous or other materials and, therefore, the wetting agentspf the invention may advantageously be used in the kier boiling of cotton, the scourin of wool, in the boiling-off of ray-on, in dyebaths, in the p oduction of sanforized cotton, in the fat- .liquoring of leather, in the treatment of paper,

and the like.

Other objects, including the provision of a novel method of producing the wetting agents of the invention, will be apparent from a consideration of the specification and the claims.

As indicated above, the wetting agents of'th'e present invention comprise the water-soluble salts of the benzoyl sulpho propionicacid esters,

the benzoyl radical being defined as a radical of "the type 'RCO Where R is a phenyl or substituted phenyl radical of the type hereinafter set forth,

The surface active agents of the present invention are represented by the formula:

where B; is selected from the g ou cons st n or hyd o en phenyl,, cyclo xy a a y gro p containing from 1 to 9 carbon atoms; where R l,

is selected from thegroup consisting of hydrogen Application October 12, 1948, er al -$47 0 2 the group consisting of phenyl and cyclohexyl radicals; whereA is selected from the group con; sisting of hydrogen and chlorine except when R'1 is an alkyl group, in other words, A is selected from the group consisting .of hydrogen and chlorine when R1 is hydrogen, and is hydrogen when H1 is an alkyl group; where R2 is selected from the group consistin of alkyl groups con,- taining from 1 to 9 carbon atoms, phenethyl, methylcyclohexyl and cyclohexyl groups; where B is an ethylene group; where M is a cation pro,- viding wateresolubility to the product; and where the total number of carbon atoms of R plus carbon atoms in the substituted groups (R1 and/or R1 .onthe phenyl nucleus is at least 8 but not more than 16., V

Thus, in the above formula, the group reaki f t n an ot e r c e 62 derivative selected from the group consisting of phenyl, monoalkyl phenyl, dialkyl phenyl, monochlorophenyl, monoalkyl monochlorophenyl, phenyl phenyl, phenyl chlorophenyl, cyclohexyl phenyl, and cyclohexyl ehlorophenyl, wherein the alkyl groups mentioned contain from 1 to 9 carbon atoms, and'wherein the number of carbon atoms supplied by substituted groups attached to the phenyl nucleus, whether an alkyl group or groups, a phenyl or cyclohexyl group, provide, with carbon atoms supplied by R2, a total of at least 8 but not more than 16 carbon atoms.

In the above formula, no attempt has been made to indicate to which of the two carbon atoms in the ethylene (B) group the sulpho group (.-SO3- ,M) is attached. The most practical-chemical processes, however, for introducing the sulpho group into this ethylene linkage are believed .to produce mixtures rather than pure alpha or pure beta derivatives. Generally, while the alpha derivative is believed to predominate, the location of the sulpho group is immaterial since it must exert a similar hydrophilic action on the moleculeeither in the alpha or the beta p osition,.and;it is .to be understood that both the alpha and beta compounds and mixtures thereof are Withinthe scope of the invention.

As pointed out in connection with the formula, M is a cation rendering the compound watersoluble, forexample, an alkali metal such as sodium or potassium, the ammonium radical, and the like.

The products of the present invention thus embody not only a benzoyl or chlorbenzoyl group but also a definite number of exterior or external carbon atoms in the various R groups. As stated, these external carbon atoms must total at least 8 and not more than 16, but no one group thereof can contain more than 9 carbon atoms, some or all of these external carbon atoms may be provided by R2, that is by the alkyl ester group or by the cyclic ester group selected from the group consisting of the phenethyl, methylcyclohexyl, and cyclohexyl groups. Some of these external carbon atoms maybe provided by a substituted group or groups attached to the phenyl nucleus, and as indicated, these substituted groups may be alkyl groups containing from 1 to 9 carbon atoms, or cyclic groups selected from the group consisting of the phenyl and cycloheXyl groups. When any of the various R groups is an alkyl group, it is relatively immaterial from the standpoint of the present inven tion whether it is a straight or branched chain alkyl group. A chlorine atom may also be attached to the phenyl nucleus without altering the properties of the compound significantly. Since no one group, whether attached to the phenyl nucleus or forming the ester group contains more than 9 carbon atoms, and since the total number of external carbon atoms ranges from 8 to 16, for each ester group (R2) employed. there is a definite range of carbon atoms that may be present in the groups attached to the phenyl nucleus and vice versa. For example, if there are no groups containing carbon atoms attached to the phenyl nucleus (i. e.

A B1 I is phenyl or monochlorophenyl) the ester groups are restricted to the octyl, nonyl, and phenethyl groups; while if, for example, a nonyl group and a hexyl group are attached to the phenyl nucleus (i. e.

A Rr I is hexylnonyl phenyl) the ester is restricted to the methyl group.

While numerous specific compounds may be prepared by the methods hereinafter described corresponding to the formula given for the compounds of the invention, they will possess marked wetting properties, making them available for use as surface active agents in the various industrial fields. This is because such compounds embody the basic structure hereinbefore set forth and contain external carbon atoms within the stated limits, and the specific examples hereinafter set forth demonstrate the fact that such compounds possess marked wetting properties.

The compounds of the invention possessing wetting properties to the highest degree are those corresponding to the formula:

where PM is an alkyl group containing from 1 to 9 carbon atoms, where R2 is an alkyl group containing from 1 to 9 carbon atoms, where B and M are as stated above, and where the total number of carbon atoms supplied by R2 and R'r is from 10 to 14. Preferably, R1 contains from 3 to 6 carbon atoms, R2 contains from 4 to 9 with a total of external carbon atoms of from 10 to 14, and M is sodium.

The products of the invention may be readily and economically prepared by condensing the desired phenyl derivative reactive in a Friedel- Crafts acylation type of reaction, with the anhydride of a four carbon atom dicarboxylic aliphatic acid, i. e. maleic anhydride or succinic anhydride: esterifying the resulting acid; and then converting the ester into the sulpho derivative, as will be further discussed hereinafter. Another, but not preferred, method of preparing the products of the present invention is by condensing a half ester-half acid chloride of the four carbon atom dibasic acid with the phenyl derivative to provide the ester, and then converting the ester into the sul ho derivative.

In preparing the benzoyl derivative, the desired phenyl d ri ative furnishing not onlv the phenyl or monoch orophenyl nucleus, but also any substituted alkyl, phen l. or cvclohexvl group, is reacted by a Friedel-Crafts acylation reaction with a molar eouivalent of the anhydride. The phenyl derivative may be obtained from any source, for instance from coal tar, petroleum or from synthetic processes. For example, in the case of alkylated phenyl derivatives, these may be obtained by condensing ben ene with an alkyl halide or with an ali hatic olefin by a preliminary Friedel-Crafts alkylation reaction.

Exam les of the phen l derivatives that may be used in the preparation of the benzoyl derivatives in accordance with the present inventions are: benzene; monochlorobenzene; the monoalkyl benzenes such as tol ene, iso'oropvl benzene (cumene) secondary but l benzene, n-butvl benzene, amyl benzene, hexyl benzene, n-octvl benzene, 2-octyl benzene, l-methyl l-ethylamylbenzene, nonyl benzene. l-nropvl 1-methylamyl- 1 benzene, and the like: the dialk l benzenes such as xylene, m thyl isopropvl benzene (cymene). secondary butyl toluene, diethyl benzene, dibutyl benzene, diamyl benzene, nonyl toluene; nonyl secondary but l ben ene, and the like: the monoalkvl monochlorobenz nes s ch as chlorotoluene, chloroc mene, secondary but l chlorobenzene. nonyl chlorobenzene, and theli e: phen l benzene, p enyl chlorben ene, cyclohexyl benzene. an cyclohexyl chlorbenzene.

The anhydride of the four carbon atom dicarboxylic ali hatic acid ma be the unsaturated maleic anhydride or the saturated succinic anhydride. When maleic anhydride is employed, the benzoyl compound prior to sulohonation is a benzovl acr lic acid ester. U'oon sulohite addition, the double bond is saturated and the product is a water-soluble salt of a benzoyl sul ho propionic acid ester, wherein the $03M group has become attached to one of the carbon atoms of the -CH=CH group, and a hydrogen atom to the other. In the case of succinic anhydride, the benzoyl derivative of propionic acid is formed as a result of the Friedel-Crafts reaction and a hydrogen atom attached either to the alpha or beta carbon atom must be substituted by the sulpho group, as hereinafter described.

The reaction between the phenyl derivative and the anhydride to form the corresponding benzoyl acrylic or propionic acid is brought about, as has been stated above, by a Friedel-Crafts rlat onreaction. and a y et he. various zen:-

hydrous or substantially anhydrous aluminum chloride. While the solvent employed may, in the case of relatively low boiling phenyl derivatives, be an excess of the phenyl derivative, the use of a suitable inert solvent such as carbon disulphide, orthodichlorobenzene, methylene chlcride, ethyl-v ene chloride, and tetrachloroethane is preferred. The phenyl derivative and the anhydride may be mixed with the solvent and the aluminum, chloride added thereto, preferably-gradually over a period of time, or the phenyl derivative may be mixed'with a portion or all of the aluminum chloride and the anhydride and-solvent may then be added, preferably gradually, followed by the addition of further amounts of aluminum chloride, if required. Other procedures for bring,- ing'together the phenyl derivative, the anhydride, the solvent, and the aluminum chloride maypoicourse be used, if desired. For example, the aluminum chlorida'anhydride, and solvent may be mixed and the phenyl derivative gradually added, thereto. The reaction, at least at the start, is exothermic and hydrogen chloride is evolved as the reaction proceeds. The reacting mixture is generally maintained at a temperature in the-range from about C. to about 65C. by cooling at the start and by heating subse: quently if necessary, and it'is advantageousto agitate the mixture duringthe reaction.

When the condensation is completed, which may be determined by ce sation of the evolution of the hydrogen chloride, the mass may be poured into ice, water, and a small amount of mineral acid, keeping the mass cold as is the usual practice in the type of reaction, and the mixture may be agitated until the aluminum chloride complex is decomposed. The condensation product which is in solution in the solvent may then be senarated from the aqueous phase and washed with water and mineral acid to remove the salts of aluminum.

The benzoyl acrylic or propionic acid may be isolated by either extracting it from the solvent with a warm 5% soda ash solution or by remove ing the solvent by distillation. The acid may be purified by dissolving it in a solutionof a suitable alkali, such as soda ash, filtering to remove any insoluble material and precipitating the acid by the addition of mineral acid.

In one procedure, the phenyl derivative is dissolved in an inert solvent and about one molecular equivalent of maleic anhydride added to the solution. The mixture is heated to a temperature at which the aluminum chloride com.- plex re in d e for e am le, t abou 10 C.,'a nd is maintained between that tempera.- ture and about 50 C. during the reaction. The aluminum chloride (about 2 molecular equiva; lents) is added gradually, for example, in portions during the reaction, and the mass is agitatedduring the reaction. When the reaction isccmplete, which may r qui se eral. h urs for e am le six h u the a uminum ch ori e comp ex s de m ose and the a id i ola d above described. j

In a more preferred procedure, the aluminum chloride, anhydride, and a Chlorinated solvent are m xe a d t e m xture is agi ated nd bep e edthe mixture. is. s red or a hort encil at a temperature between about C. and about,

so? 0.. The alumin or de c m l x is dec mpos d. a d the c d, olate s a o eescribed.

Ihe benczoyl acrylic or propionic acid is, esterified with a c m ou d o i n t red R2. roup. nd t e result n ster is hen 1k verted to th sul bo deri t e The e e 01? t e aci ma be re ar dby a yo he sui abl stsr iv ne reaeticnsi In one type of method, the ester may be {or-med icy-reactin the a d with one m e u ar e i s et o the alcoh co es di o h er des red n he pre e ce o a Solvent and a t i-"i fying catalyst such as concentrated sulphuric acid, benzenee or toluene-sulphonic acid. Pref-,- erably, the solvent is one which like toluene, boils slightly above the boiling point of water. The mixture of the benzoyl acrylic or propionic acid, the alcohol, the solvent and the esterification catalyst are boiled and the water formed by the esterification reaction is removed. After the es terification reaction has been completed, the es-. ter, which is in solution in the solvent, may be Washed with water, followed in some cases by dilute alkali to remove any unconverted acid and the traces of catalyst. The ester may be isolated by removing the solvent by steam distillation, di s: tii ation t a o he c res ure o b ven: orat n in acuo- In another type of esterification procedure to produce c m un i h ch R s a S a l alkyl rou the e te o t e ben yl cr li or r i nic aci may be btained by dis o in t ac d in a s en iich tolu ne be ze chlo enze e. orthodichlorobenzene, carbon tetrachloride, tet-. rachlorethane, and the like. The acid is then converted into a salt and the ester formed by reaction an alkyl sulphate, the alkyl g oup .of which corresponds to the ester desired. In such a proc: ess, the salt is advantageously Ormed by the ad dition of a slurry of soda ash in water, and in such a case, foaming occurs due to the evolution of carbon dioxide, and the mass becomes thick and hasthe appearance of a clear gel. The reaction between the salt of the acid and the alkyl S111? phate is exothermic and is completed within a few minutes, as shown by the fact that a sample mixed with water separates readily into two layers. The mass obtained as the result of the re.- ecticn is ma e a isi b t e a d tio o ine a aci i wa h d ith w ter ie o h a ts and the ester is ob a ned upon r a of h ol e by cam or vacuum d s a cn- The enz i acryl c or pro ionic a i t r may be converted into the sulpho derivative by an y process by which the..-.-.-$.O ,.-M group maybe attachedtc one of the carbon atoms of the vinylene or-ethy-lene chain of "the acrylic or propionic acid ester. Preferably, when a 'benzoyl acrylic acid ester is employed, the sulphonation is r u h a out by rea ing t e r ith a bi ii nhi e su as cd m. o as ium or n;-

moniu n bi il i in t e sulnhonat en te a e s. th e t r i mixed with e is i ph disss es in wa er crot e so ent a r sam le a m tu e of eq a a ts o ater-end ei y 'la coho The sulphite employed issufficient to convert the ester into thesodium or other salt of 'ihes pi c ic acid; h us o a liiex s f the hin bii sfies be ng ,a venia avin- The mixture is advantageously heated in a closed container equipped with an agitator until the ester becomes completely soluble in water. The temperature of heating will depend on the particular ester being treated and usually a temperature between about 80 C. and 110 C. will be employed, and in many instances it will be desirable to heat the mixture to boiling. The ester is rendered completely soluble in water by this treatment and the product formed is the sulphonic acid salt of the cation of the bisulphite. Thus, as stated in connection with the formula, -M may be any cation which provides watersolubility, for example, an alkali metal ion, ammonium radical, or the like.

Referring to the saturated benzoyl propionic acid ester, it may be first converted into a halogenated derivative, for example, a bromo compound, prior to sulphonation. In such conversion process, the ester is advantageously dissolved in a solvent and a small amount of a halogenating catalyst such as phosphorus trichloride is added. The halogen, for example, bromine, is then brought into contact with the solution, for instance, by adding liquid bromine drop-by-drop to the solution. Hydrogen halide isliberated and the reaction is completed in a short time. The halogenated derivative is isolated by evaporation of the solvent. The halogenated derivative thus prepared may then be sulphonated by reacting the halogen derivative with a sulphite, for example, sodium or potassium sulphite, to replace the halogen atom of the compound with the SO3M group. Ad-

vantageously, the reaction is brought about by refluxing an aqueous mixture of the reactants until the reaction has progressed to completion. As in the case of the products obtained by the previously described method of sulphonation, the sulphonated product may be provided with the desired cation represented by M.

In order to illustrate the invention further, the following specific examples are given for the preparation of the compounds of the present invention. Four different procedures were employed in preparing the compounds of the examples, three of which are illustrated below as Methods A, B, and C, respectively. Each of the numerical examples, from 1 to 47, inclusive, were made according to one of these three methods and to avoid repetition of the details of the procedures, each of these examples is designated as to which method was followed. In each case, a measure of the compounds surface activity is given by showing wetting speeds at various concentrations in water determined by the time required to wet out a 5 gram skein of raw cotton yarn at 100 F. according to the standard Draves method. Example 48 illustrates the fourth method.

METHOD A 'The preparation of the methyl ester of 2-nonylbenzoyl sulpho propionic acid, sodium salt Toa mixture of 49 g. mol) of maleic anhydride and 105 g. aluminum chloride, there are added 90 cc. ethylene chloride. The suspension is agitated and water cooled. After most of the solids have dissolved, 102 g. mol) 'of Z-nonyl benzene are added slowly. After the addition. the mixture is stirred for 30 minutes at 50C The material is then cooled and decomposed with a mixture of 450 g. crushed ice, 50 cc. of 66% sulphuric acid and cc. isopropanol. After most of the dark brown complex has been decomposed, the mixture is heated to reflux temperature. After .five minutes of refluxing, the material is split. The lower layer is discarded. The upper layer is then washed twice with '70 cc. portions of 66% sulphuric acid. 17 cc. of methanol and 12 cc. of concentrated sulphuric acid are added to the ethylene chloride solution of the maleic anhydride condensate and the material is' refluxed for 45 minutes. The lower layer is then drawn off and another 12 cc. of methanol and 8 cc. of concentrated sulphuric acid are added, and

temperature is maintained there for one hour al-- though the sulphonation reaction is usually completed after ten minutes. wetting speed of 32 seconds. at a concentration of .1%.

METHOD B The preparation of the Z-ethylhemyl ester of sec. batylbenzoyl sulpho propionic acid, sodium salt To a mixture of 49 g. mol) maleic anhydride and 105 g. aluminum chloride, there are added cc. of ethylene chloride. The suspension is agitated and water cooled. After most of the solids have dissolved, 67 g. mol) sec. butylbenzene are added slowly. After the addition, the mixture'is stirred for 30 minutes at 50 C. The material is then cooled and decomposed with a mixture of 500 g. crushed ice, cc. 66% sulphuric acid and 65 g. mol) 2-ethylhexanol. The mixture is stirred for 90 minutes at room temperature. The lower layer is then drawn off. 1 cc. of concentrated sulphuric acid is added to the organic layer which is then refluxed through a constant Water separator for 2 hours or longer until practically all of the acid has been esterifled. The solvent is distilled off until the temperature within the oil has reached C. A solution of 52 g. sodium bisulphite and 1 g. sodium hydroxide in 110 cc. of water is added to the oil. The agitated mixture is heated to 105 C. and is maintained there for 15 minutes, after which time sulphonation' is complete. The isolated product at a concentration of 0.1% in water, provided a wetting speed of 2 seconds.

METHOD C The preparation of Z-ethylhercyl ester of tert. butylbenzoyl sulpho propz'onic acid, sodium salt To a cooled and stirred mixture of 49 g. mol) maleic anhydride, 67 g. /2 mol) tert. butyl benzene and 300 cc. o-dichlorobenzene, there are added gradually in small portions g. aluminum chloride. The temperature is allowed to rise slowly to 50 C.-60 C. where it is maintained until no more hydrogen chloride is given off. The material is decomposed by pouring it over 1 kg. of crushed ice to which 100 cc. of concentrated sulphuric acid has been added. The mixture is stirred until the aluminum chloride complex has been broken up completely. Then the lower layer is drawn off and the solvent is steamdistilled off from the upper layer. The steam distillation residue is taken up in a mixture of 200 cc. of toluene and 70 g. 2-ethylhexanol' and The product gave a toluene being returned to the mixture, until practically all of the acid is este'rified which requires about 4 hours. The bottom layer is thendrawn off and any mineral acid present in the oil is neutralized. The toluene is steam-distilled oil. The ester is then 'sulphonated as described under Method B. The product gaves a wetting speed of seconds at a concentration of 0.1%.

Other water-soluble salts instead of the sodium salts, such as-the potassium or ammonium salts, may be prepared byemploying potassium or ammonium bisulphite in the above methods in place of sodium bis-ulphite. These other water- -"sol'uble salts exhibit strong surface active properries, and may be used in a manner similar to 'the sodium salts.

In the following examples, the sodium saltof the benzoyl sulpho propionic acid esters is prepared, but as previously set forth, other watersoluble salts such as the potassium or the ammonium-salts may be prepared by analogous pro- 'cedures. 7

EXAMPLE -1 The salt of the 2-ethyl hexyl ester of benzoyl .sulpho propionic acid was prepared following Method 0, by first condensing benzene with-maleic anhydride. The benzoyl acrylic acid thus formed was esterii'led with 2-ethy1 hexyl acohol, and the resulting ester was reacted with sodium .bisulphite to form the sulpho derivative. At a concentration of 12%, the compound gave a wetting speed of only 7 seconds, and at .1% a wetting speed of 120 seconds. 7

7 EXAMPLE 2 The salt of the Z-ethyl hexyl ester of chloro formed was esterifie'd with 2-ethyl hexyl alcohol 5 and the resulting ester was reacted with sodium bisulphite to-formthe sulpho derivative. This *compound provided a wettingspeed-of 27 seconds at a concentration of .1%.

- The salt of the 2-ethyl hexyl ester of chlorot'oluioyl sulpho propionic acid was prjoared'following Method B, by first condensing monochloro toluene with maleic anhydride. The chimtoluoyl acrylic acid thus formed was est'erified with Z-ethyl hexyl alcohol and the resulting ester was reacted with sodium bisulphite to form the 'sulpho derivative. At a concentration of only .05%, it' 'provided 'awe'tting speed of 15.5 seconds, and at .03%, 131 seconds.

. EXAMPLE 5 i The saltof the n hexyl esterof xyloyl s'ulpho propionic' acid was prepared -following' -Method B, by first condensingxyl-ene with maleic anhydride. The xyloyl acrylic acid thus formed was est'er'ified'with n-hexylalcohol and the resulting ester'was reacted with sodium bisulphite to form the sulphojderivative. This compound provided awettin'g speed of'81 seconds at a concentration EXAMPLE 6 The salt of theZ-ethyI hexyl ester of xyloyl sul ho propicnic "acid was prepared following Method B, by first condensing Xylene with maleic anhydride. The'Xyloyl-acrylic acid thus formed was esterified with 2-ethyl hexyl alcohol and the resulting ester. was reacted with sodium bisulphite to form the sulpho derivative. This com- .pound provided a wetting speed of 48seconds at a concentration of only .05

1t 'i PL'E 7 The salt of the {2-ethy1butyl ester of cumenoyl '(isopropyl benzoyl) sulpho propionic-acid was prepared following Method C, by first condensing cumene with maleic anhydride. The cumenoyl acrylic acid thus formed was esterified with '2-'ethy1 butyl alcohol and the resulting ester =-was reactedwith sodium-bisulphite to form th'e'sulp'h'o derivative. A wettin'g speed of seconds was provided by this-compound at a concentration-of 2 ,-and T65 seconds at .1%.

'IEXAMPIES;

The salt' of the n-ihexyl ester of cumenoyl sulpho propionic acid was prepared following Method C, by first condensing cumene with maleic anhydride. "The cumenoyl acrylic acid thus :formed was :esterified with n-hexyl 'alcdhol, "and'the resulting ester was reacted with-sodium sbisulphite to iforim the sulpho-derivative. .Ata concentration of .2%, thislcompound provideda speed of 120 seconds.

*thus formed-was esterified with n -heptyl alcohol, and the resulting'ester was reacted with sodium bisulphi-te to form the sulpho derivative. It gave a wetting speed -of5- seconds a t-a concentration of .2%,-and 28 seconds at .1

EXAMPLE 1 0 v The salt of the 2- ethyl hexyl ester of cumenoyl sulpho. propionic acid was prepared fol-lowing Method C, by first condensing cumenewith-maleic anhydride. The cumenoyl acrylic acid thus formed was esterified with 2-ethyl hexyl alcoholand the resultingester was reacted withsodlum bisulph-ite to form the sulpho derivative. It (gave --a wetting speed of 24 seconds-at -a concentration of only .05%,-, and seconds at only EXAMPLE 11 The salt oi? the Z-et'hyl hexyl 'ester of chloro- -cumeno 1 sulpho propionic acid was preparedfollowing MethodB, by first -condn'sihg monoclil'orocumene with :maleic anhydride. The chlorocumenoyl acrylic acid thus formed was esterified I with -2-etliyl hexyl alcohol and the resu'lting ester v was reacted with sodium lo'i'sulphite to form the sulpho derivative. :It gave a wettingspeed of '29 seconds at a concentration of i0'3%, and 153-secendsst 2029.

'-with maleic anhydride.

" sulphite to form the sulpho derivative.

: derivative.

.. benzene with maleic anhydride.

11 EXAMPLE 12 The salt of the n-octyl ester of sec. butylbenzoyl sulpho propionic acid was prepared using Method B, by first condensing sec. butyl benzene The sec. butyl benzoyl acrylic acid thus formed was esterified with noctyl alcohol and the resulting ester was reacted with sodium bisulphite to form the sulpho derivative. It gave a wetting speed of 33 seconds at a concentration of only .02%, and 67 seconds at only .015%.

EXANIPLE 14 The salt of the 2-ethyl hexyl ester .of l-butyl- .benzoyl sulpho propionic acid was prepared following Method C, by first condensing l-butyl benzene with maleic anhydride. The butylbenzoyl acrylic acid thus formed was esterified with 2-ethyl hexyl alcohol, and the resulting ester was reacted with sodium bisulphite to form the lsulpho derivative. It gave a wetting speed of 80 seconds at a concentration of only .025%.

EXAMPLE 15 The salt of the 2-ethyl hexyl ester of cymenoy'i v (l-methyl-l-isopropyl benzoyl) sulpho propionic acid was prepared following Method B, by first condensing cymene with maleic anhydride. The cymenoyl acrylic acid thus formed was esterified with 2-ethyl hexyl alcohol, and the resulting ester was reacted with sodium bisulphite to form the sulpho derivative. It gave a wetting speed "of'20 seconds at a concentration of .03%, and 127 seconds at 02%;

EXAlVDPLE 16 The salt of the Z-ethyl hexyl ester of sec. butyl chlorobenzoyl sulpho propionic acid was prepared following Method B, by first condensing I sec.-butylchlorobenzene with maleic anhydride.

The but-y! chlorbenzoyl acrylic acid thus formed was esterified with 2-ethyl hexyl alcohol, and the resulting ester was reacted with sodium bi- It ave a wetting speed of 53 seconds at a concentration of only .02

. EXAMPLE 17 The salt of the 'n-butyl ester of sec. amylbenzoyl sulpho propionic acid was prepared following Method B, by first condensing sec. amyl benzene with maleic anhydride. The amylbenzoyl acrylic acid thus formed was esterified with n-butyl alcohol and the resulting ester was reacted with sodium bisulphite to form the sulpho It gave a wetting speed of 140 seconds at a concentration of .05%.

EXAMPLE 18 The salt of the 2'- ethyl hexyl ester of sec. amyl-- benzoyl sulpho propionic acid was prepared following Method B, by first condensing sec. amyl The amylbenzoyl acrylic acid thus formed was esterifiedwith robenzoyl' sulpho propionic acid was prepared 12 '2-ethyl hexyl alcohol, and the resulting ester was reacted with sodium bisulphite to form the sub pho derivative. It gave a wetting speed of 25 seconds at a concentration of only .02%.

EXAMPLE 19 The salt of the n-nonyl ester of n-heptylbenzoyl sulpho propionic acid was prepared following Method. B, by first condensing n-heptylbenzene with maleic anhydride. The heptylbenzoyl acrylic acid thus formed was esterified with nnonyl alcohol, and the resulting ester was reacted with sodium bisulphite to form the sulpho derivative. At a concentration of .1%, the compound gave a wetting speed of 35 seconds.

EXAMPLE 20 The salt of the n-heptyl ester of nonylbenzoyl (1,3,5 trimethyl hexylbenzoyl) sulpho propionic acid was prepared following Method B, by first condensing nonyl (1,3,5 trimethylhexyl benzene) benzene with maleic anhydride. The nonyl benzoyl acrylic acid thus formed was esterified with .n-heptyl alcohol and the resulting ester was reacted with sodium bisulphite to form the sulpho derivative. It gave a wetting speed of 28 seconds at a concentration of .1%.

EXAMPLE 21 The salt of the methyl ester of n-heptylben-- zoyl sulpho propionic acid was prepared following Method A, by first condensing n-heptylbenzene with maleic anhydride. The heptylbenzoyl acrylic acid thus formed was esterified with methyl alcohol, and the resulting ester was reacted with sodium bisulphite to form the sulpho derivative. At a concentration of .1%, the compound gave a wetting speed of seconds EXAMPLE 22 The salt of the n-hexyl ester of 2-nonyl chlofollowing'Method B, by first condensing 2-nonyl chlorobenzene with maleic anhydride. The nonyl chlorobenzoyl acrylic acid thus formed was esterified with n-hexyl alcohol, and the resulting ester was reacted with sodium bisulphite to form the sulpho derivative. It gave a wetting speed of 35 seconds at a concentration of .15%.

EXAMPLE 23 The salt of the methyl ester of 2-nonyltoluoyl sulpho propionic acid was prepared following Method A, by first condensing 2-nonyl toluene with maleic anhydride. The nonyl toluoyl acrylic acid thus formed was esterified with methyl alcohol, and the resulting ester was reacted with sodium bisulphite to form the sulpho derivative.

It gave a wetting speed of 7 seconds at a concentration'of 0.2%.

EXAMPLE 24 The salt of the 2-ethyl hexyl ester of sec.-butyl toluoyl sulpho propionic acid was prepared following Method B, by first condensing sec.-butyl toluene with maleic anhydride. The sec.-butyl toluoyl acrylic acid thus formed was esterified with 2-ethyl hexyl alcohol, and the resulting ester was reacted with sodium bisulphite to form the sulpho derivative. It gave a wetting speed 01' instantaneous at a concentration of .2%.

EXAMPLE 25 The salt of the ethyl ester of diamyl benzoyl sulpho propionic acid was prepared following Method A, by first condensing diamyl benzene (technical di-sec. amyl benzenelwith maleic anhydride. The diamyl benzoyl acrylic acid thus tormed was esterified with ethyl alcohol, and the resulting ester was reacted with sodium bisulphite to form the sulpho derivative. Itgave a wetting speed of seconds at a concentration of .2%', and 45 seconds at .1%. a

" EXAMPLE 26 The salt of the hexyl ester of diarnyl benzoyl sulpho propionic acid was prepared following Method C, by first condensing diamyl benzene (technical di-sec. amyl benzene) with maleic an- Ihydride. The diamyl benzoyl acrylic acid thus formed was esterified with hexy1 ,a1 cohol, and the resulting ester wasreacted with sodium bis'ulphite to form the sulpho derivative lt gave awetting speed of 10 seconds ata concentration of. 2%. 7

EXAMPLE 2'7 A, v by first condensing nonyl 1,3,5 trime thyl 'hexyl) secondary butyl benzene with maleic anhydride. The nonyl secondary butyl benzoyl acrylic acid thus formed was esterified with npropyl alcohol, and the resulting ester was reacted with sodium bisulphite to form the sulpho derivative. At a concentration of .05%, it gave a wetting speed of 46 seconds.

EXAMPLE 2s The salt of the n-nonyl ester of diethylbenzoyl sulpho propionic acid was prepared following Method B, by first condensing diethylbenzene with maleic anhydride. The diethylbenzoylacrylic acid thus formed was esterified with nn'onyl alcohol and the resulting ester was treated with sodium bisulphite to form the sulpho derivative. At a concentration of 135% the compound gave a wetting speed of seconds.

EXAMPLE 29 v The salt of the ethyl ester of phenylbenzoyl sulpho, propionic acid was prepared following Method A, by first condensing phenylbenzene 'with maleic anhydride. The .phrii'lbehz'oyl acrylic acid. thus formed was esterified with ethyl alcohol, and the resulting ester was reacted with sodium bisulphite to form the sulpho derivative. At a concentration of (1.2%, the compound gave a wetting speed of 70 seconds.

EXAMPLE 30 The salt of the 2-ethy1 heXyl ester of phenyl benzoyl sulpho propionic acid was prepared fol- .lowing Method B, by first condensing-..phenyl benzene with maleic anhydride. The phenyl .rderivative. At a concentration of .0.Q5%. this compound gave a wetting s'peed 'o'f'35' seabirds i4 EXAMPLE The salt of the ethyl ester of cyclohexylben zoyl sulpho propionic acid was prepared following Method A, by first condensing cyclohexylbenzene with maleic anhydride. The cyclohexylbenzoyl acrylic acid thus formed was esterified with ethyl alcohol and the resulting ester was reacted with sodium bisulphite to form the sulpho derivative. At a concentration of 0.3%, the compound gave a wetting speed of 30 seconds. H EXAMPLE-33 The salt of the 2-ethylh'exyl ester of cyclo' hexyl benzoyl sulpho prdpioriic acid was pre-- pared following Method B, by first condensing cyclohexyl benzene with maleic anhydride. The cyclohexyl benzoyl acrylic acid thus formedwas esterified with 2-ethy1 hexyl alcohol and -the resulting ester was reacted with sodium bisulphite to form the sulpho derivative. At a concentration of .l%, it gave a wettingspeed of 8 seconds.

EXAMPLE 34 z The salt of the n-nonyl ester of cyclohexylhenzoyl sulpho propionic acidwas prepared by Method B, by first condensing cycloliexylbe'nzone with maleic anhydride. The cyclohexylbenzoyl acrylic acid thus formed wasesterified with n-nonyl alcohol, and the resulting ester was reacted with sodium bisulphite to form the sulpho derivative. At aconcentration of 0.1%,

it gave a wetting speed of 35 seconds;

EXAMPLE 35 The salt of the cyclohexyl ester of ethylben'zoyl sulpho propionic acid was prepared by Method B, by first condensing ethyl benzene with maleic anhydride. The ethylbenzoyl acrylic acid thus formed was esterified with cyclohexanol, and the resulting ester was reacted with sodium bisulphite to form the'sulpho derivative. At a concentration of 0.2 the compound gave a wetting speed of 20 seconds.

EXAMPLE 36 The salt of the cyclohexyl ester of sec.-buty lchlorbenzoyl sulpho propionic acid was prepared following Method B by first condensing sec -butyl chlorbenzene with maleic anhydride.. The sec.- butylchlorbenzoyl acrylic acid thus formed was esterified with cyclohexanol, and the resulting ester wasreacted with sodium bisulphite to form the sulpho derivative. At 'a concentration of 9.95%, the compound gave a wetting speed of 60' seconds. V I EXAMPLE 37 The salt of the cyclohexyl ester of nonylbenzoyl (1,3,5 trimethylhexyl benzoyl) sulpho propionic acid was prepared following Method B, by first condensing nonylbenzene (1,3;5 trimethylhexylbenzenel with maleic anhydride. The nonylbenzoyl acrylic 'acid thus formed was esterified with cyclohexanol, and the resulting ester was reacted with sodium bisulphite to form the sulpho derivative. At a concentration "of 0.2%, the compound gave a wetting speed of 25 seconds.

EXAMPLE 38 7 The salt of the methylcyclohexyl ester of toluoyl sulpho propionic acid was prepared following Method B by first condensing toluene with maleic anhydride. The toluoyl acrylic acid thus'formed was esterified with methylcycleh ekanol and-the id resulting ester was reacted with sodium bisulphite to form the sulpho derivative. At a concentration of 0.2%, the compound gave a wetting speed of 45 seconds.

EXAMPLE 39 The salt of the methyl cyclohexyl ester of sec.- butyl benzoyl sulpho propionic acid was prepared following Method B, by first condensing sec.-butyl benzene with maleic anhydride. The sec.-butyl benzoyl acrylic acid thus formed was esterified with methyl cyclohexyl alcohol, and the resulting ester was reacted with sodium bisulphite to form the sulpho derivative. At a concentration of 115%, it gave a wetting speed of 11 seconds.

EXAMPLE 40 -The salt of the methylcyclohexyl ester of phenylbenzoyl sulpho propionic acid was prepared following Method B, by first condensing phenylbenzene with maleic anhydride. The phenylbenzoyl acrylic acid thus formed was esterified with methylcyclohexanol, and the resulting ester was reacted with sodium bisulphite to form the sulpho derivative. At a concentration of 0.1%, the compound gave a wetting speed of 20 seconds.

EXAMPLE 41 The salt of the methylcyclohexyl ester of cyclohexylbenzoyl sulpho propionic acid was prepared following Method B, by first condensing cyclohexylbenzene with maleic anhydride. The cyclohexylbenzoyl acrylic acid thus formed was esterified with methylcyclohexanol, and the resulting ester was reacted with sodium bisulphite to form the sulpho derivative. At a concentration of 0.1%, the compound gave a wetting speed of 65 seconds.

EXAll/LPLE 42 The salt of the B-phenethyl ester of chlorbenzoyl sulpho propionic acid was prepared following Method B, by first condensing chlorbenzene with maleic anhydride. The chlorbenzoyl acrylic acid thus formed was esterified with B-phenethyl alcohol, and the resulting ester was reacted with sodium bisulphite to form the sulpho derivative. At a concentration of 0.2%, the compound gave a wetting speed of 85 seconds.

EXADHPLE 43 The salt of the B-phenethyl ester of sec.- butylbenzoyl sulpho propionic acid was prepared following Method B, by first condensing sec.- butylbenzene with maleic anhydride. The sec.- butylbenzoyl acrylic acid thus formed was esterified with B-phenethyl alcohol, and the resulting ester was reacted with sodium bisulphite to form the sulpho derivative. At'a concentration of .1%, it gave a wetting speed of 32 seconds.

EXAMPLE 44 The salt of the B-phenethyl ester of octylbenzoyl (l-methyl l-ethyl amylbenzoyl) sulpho propionic acid was prepared following Method B, by first condensing octylbenzene (l-methyl l-ethyl amylbenzoyl) with maleic anhydride. The octylbenzoyl acrylic acid thus formed was esterified with B-phenethyl alcohol, and the resulting ester was reacted with sodium bisulphite to form the sulpho derivative. At a concentration of 0.3%, the compound gave a wetting speed of 35 seconds.

The alt of the B-phenethyl ester of cyclohexylbenzoyl sulpho propionic acid was prepared following Method B, by first condensing cyclohexylbenzene with maleic anhydride. The cyclohexylbenzoyl acrylic acid thus formed was esterified with B-phenethyl alcohol, and the resulting ester was reacted with sodium bisulphite to form the sulpho derivative. At a concentration of 0.2%, the compound gave a wetting speed of 90 seconds.

EXAMPLE 47 The salt of the B-phenethyl ester of benzoyl sulpho propionic acid was prepared following Method B, by first condensing benzene with maleic anhydride. The benzoyl acrylic acid thus formed was esterified with B-phenethyl alcohol, and the resulting ester was reacted with sodium bisulphite to form the sulpho derivative. At a concentration of 0.3%, the compound gave a wetting speed of 75 seconds.

EXAMPLE 48 The preparation of the propyl ester of sec. amyZ benzoyl sulpho propionic acid, sodium salt Amyl benzoyl propionic acid is prepared by condensing 37 grams of sec. amyl benzene with 27 grams of succinic anhydride in 110 cc. of orthodichlorobenzene using .64 gram of anhydrous aluminum chloride as the condensing agent.

The sodium salt of the resulting acid is made by adding 5.2 grams of soda ash and 4 grams of water to 24 grams of the acid dissolved in 60 cc. of toluene. The sodium salt is then converted to the propyl ester by the addition of 16.9 grams of dipropyl sulphate at 70 C. After one-half hour, theresterification is complete. The product is isolated after washing by distilling to remove the toluene.

The propyl ester of amyl benzoyl propionic acid is brominated by adding 2'7 grams of dried bromine to 38 grams of the ester in 50 cc. of carbon tetrachloride, using 0.25 cc. of phosphorus trichloride as a catalyst. The bromine is added dropwise at 50 C. to the ester. Hydrogen bromide is liberated and the reaction is complete in a short time. The solvent is evaporated in vacuo.

The above bromo compound is heated with sodium sulphite to give the sulpho derivative, for

. example 39 grams of the bromo ester and 27 grams of sodium sulphite in 2'7 grams of water are refluxed five hours. The mass is diluted with water to give a clear brown solution containing 10% of the product based on the theoretical yield. A portion of the solution was diluted to 0.2% and gave a wetting speed of 50 seconds.

Of the foregoing compounds, the water soluble salts of the octyl ester of butylbenzoyl sulpho propionic acid and more specifically the sodium salt of Z-ethyl hexyl ester of sec. butylbenzoyl sulpho propionic acid or the sodium salt of the Where R1 is selected from the group consisting of hydrogen, phenyl, cyclohexyl, and alkyl groups containing from 1 to 9 carbon atoms; where R'i is selected from the group consisting of hydrogen and alkyl groups containing from 1 to 9 carbon atoms when R1 is selected from the group consisting of hydrogen and said alkyl groups, and where R1 is hydrogen when R1 is selected from thegroup consisting of phenyl and cyclohexyl radicals; where A is selected from the group consisting of hydrogen and chlorine when R1 is hydrogen, and is hydrogen when R1 is said alkyl group; where R2 is selected from the group con:- sisting of alkyl groups containing from 1 to 9 carbon atoms, phenethyl, methylcyclohexyl and cyclohexyl groups; where B is an ethylene group; where M is a cation providing water solubility. to the product; and where the total number "of carbon atoms of R2 plus carbon atoms in R1 and R'1 is at least 8 but not more than 16.

2. The pr'oductof claim 1 wherein M is sodiuin. 3. As a surface active agent possessing marked wetting properties, a water soluble salt of a benzoyl sulpho propionic acid ester correspon'd- I ing to the following formula:

0 o Q qz- -om R; soar where R'1 is an alkyl group containing from 1 to 9 carbon atoms; where R2 is an alkyl group containing from 1 to 9 carbon atoms; where B is an ethylene group; where M is a cation providing water solubility to the product, and where :the total number of carbon atoms supplied by Re and R'1 is from 10 to 14.

4. The product of claim 3 wherein M is sodium.

5. The product of claim 3 wherein R1 contains from 3 to 6 carbon atoms; wherein R2 contains from 4 to 9 carbon atoms, and wherein M is sodium.

6. As a surface active agent possessing marked wetting properties, a water soluble salt of an octyl ester of butylbenzoyl sulpho propionic acid.

7. As a surface active agent possessing marked wetting properties, the sodium salt of the 2 ethylhexyl ester of secondary butylbenzoyl sulpho propionic acid.

8. As a surface active agent possessing marked wetting properties, the sodium salt of the normal octyl ester of secondary butylbenzoyl sulpho propionic acid.

9. As a surface active agent possessing marked wetting properties, a water soluble salt of an octyl ester of amylbenzoyl sulpho propionic acid.

10. As a surface active agent possessing marked wetting properties, the sodium salt of the 2- ethylhexyl ester of secondary am'ylbenzoyl sulpho propionic acid.

11. The method of preparing a surface active agent possessing marked wetting properties which comprises condensing, in a Friedel-Crafts acylation reaction, a phenyl derivative selected from the group consisting of benzene, monochlorbenzene, monoalkylbenzene, monoalkylmonochlorbenzene and dialkylbenzene, the alkyl groups of which contain from 1 to 9 carbon atoms, phenylbenzene, phenylchlorbenzene, cyclohexylbenzene and cyclohexylchlorbenzene with maleic anhydride to form the corresponding benzoyl acrylic acid, esterifying the resulting acid with an esterifying compound providing an ester group selected from the group consisting of an alkyl group containing from 1 to 9 carbon atoms, a benzyl group, a phenethyl group, a methylcyclohexyl group and a cyclohexyl group, said esterifying compound being selected to provide an ester group which supplies, along with carbon atoms supplied by substituted groups on the phenyl nucleus of said phenyl derivative, a total REFERENCES CITED The following references are of record in the file of this patent: I

Bogert et a1.: J. A. C. S., vol. 47, pp. 526-535 (1925). 

1. AS A SURFACE ACTIVE AGENT POSSESSING MARKED WETTING PROPERTIES, A WATER SOLUBLE SALT OF A BENZOYL SULPHO PROPIONIC ACID ESTER CORRESPONDING TO THE FORMULA: 